New Selective Synthesis of Dithiaboroles as a Viable Pathway to Functionalized Benzenedithiolenes and Their Complexes

作者：Schlindwein Simon H; Bader Katharina; Sibold Carlo; Frey Wolfgang; Neugebauer Petr; Orlita Milan; van Slageren Joris; Gudat Dietrich^*

来源：Inorganic Chemistry, 2016, 55(12): 6186-6194.

DOI：10.1021/acs.inorgchem.6b00821

A synthetic protocol to synthesize 2-bromobenzo-1,3,2-dithiaboroles in one step from easily accessible benzene bis(isopropyl thioether)s has been developed. The reaction is remarkably specific in converting substrates with two adjacent (PrS)-Pr-i moieties while leaving isolated thioether functions and other functional groups intact. On the basis of the spectroscopic detection or isolation of reaction intermediates, a mechanistic explanation involving a neighbor group-assisted dealkylation as a key step is proposed. The resulting products featuring one or two dithiaborole units were isolated in good yields and fully characterized. Subsequent methanolysis, which was carried out either as a separate reaction step or in the manner of a one-pot reaction, gave rise to functionally substituted benzenedithiols. The feasibility of a methylphosphoryl-substituted benzenedithiol to act as a dianionic S,S-chelating ligand was demonstrated with the formation of paramagnetic Ni(III) and Co(III) complexes. Selective reduction of the phosphoryl group afforded a rare example of a phosphino dithiol which was shown to act as a monoanionic P,S-bidentate ligand toward Pd(II). All complexes were characterized by spectral data and X-ray diffraction studies, and the paramagnetic ones also by superconducting quantum interference device magnetometry.

• 出版日期2016-6-20